Tuning the Swing Effect by Chemical Functionalization of Zeolitic Imidazolate Frameworks

Claire L. Hobday, Thomas D. Bennett, David Fairén-Jiménez, Alexander J. Graham, Carole A Morrison, David R. Allan, Tina Duren, Stephen A. Moggach

Research output: Contribution to journalArticle

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Abstract

Many zeolitic imidazolate frameworks (ZIFs) are promising candidates for use in separation technologies. Compris-ing large cavities interconnected by small windows they can be used, at least in principle, as molecular sieves where molecules smaller than the window size are able to diffuse into the material while larger are rejected. However, “swing effect” or “gate open-ing” phenomena resulting in an enlargement of the windows have proven to be detrimental. Here, we present the first systematic ex-perimental and computational study of the effect of chemical func-tionalisation of the imidazole linker on the framework dynamics. Using high-pressure (HP) single-crystal X-ray diffraction, density functional theory, and grand canonical Monte Carlo simulations, we show that in the isostructural ZIF-8, ZIF-90 and ZIF-65 func-tional groups of increasing polarity (-CH3,-CHO, -NO2) on the im-idazole linkers provide control over the degree of rotation and thus the critical window diameter. On application of pressure, the sub-stituted imidazolate rings rotate resulting in an increase in both pore volume and content. Our results show that the interplay between the guest molecules and the chemical function of the imidazole linker is essential for directing the swing effect in ZIF frameworks and therefore the adsorption performance.
LanguageEnglish
Pages382-387
JournalJournal of the American Chemical Society
Volume140
Issue number1
Early online date11 Dec 2017
DOIs
StatusPublished - 10 Jan 2018

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Tuning
Pressure
Molecules
Molecular sieves
X-Ray Diffraction
Adsorption
Density functional theory
Single crystals
Technology
X ray diffraction
imidazole
Monte Carlo simulation

Cite this

Hobday, C. L., Bennett, T. D., Fairén-Jiménez, D., Graham, A. J., Morrison, C. A., Allan, D. R., ... Moggach, S. A. (2018). Tuning the Swing Effect by Chemical Functionalization of Zeolitic Imidazolate Frameworks. DOI: 10.1021/jacs.7b10897

Tuning the Swing Effect by Chemical Functionalization of Zeolitic Imidazolate Frameworks. / Hobday, Claire L.; Bennett, Thomas D.; Fairén-Jiménez, David; Graham, Alexander J.; Morrison, Carole A; Allan, David R.; Duren, Tina; Moggach, Stephen A.

In: Journal of the American Chemical Society, Vol. 140, No. 1, 10.01.2018, p. 382-387.

Research output: Contribution to journalArticle

Hobday, CL, Bennett, TD, Fairén-Jiménez, D, Graham, AJ, Morrison, CA, Allan, DR, Duren, T & Moggach, SA 2018, 'Tuning the Swing Effect by Chemical Functionalization of Zeolitic Imidazolate Frameworks' Journal of the American Chemical Society, vol. 140, no. 1, pp. 382-387. DOI: 10.1021/jacs.7b10897
Hobday CL, Bennett TD, Fairén-Jiménez D, Graham AJ, Morrison CA, Allan DR et al. Tuning the Swing Effect by Chemical Functionalization of Zeolitic Imidazolate Frameworks. Journal of the American Chemical Society. 2018 Jan 10;140(1):382-387. Available from, DOI: 10.1021/jacs.7b10897
Hobday, Claire L. ; Bennett, Thomas D. ; Fairén-Jiménez, David ; Graham, Alexander J. ; Morrison, Carole A ; Allan, David R. ; Duren, Tina ; Moggach, Stephen A./ Tuning the Swing Effect by Chemical Functionalization of Zeolitic Imidazolate Frameworks. In: Journal of the American Chemical Society. 2018 ; Vol. 140, No. 1. pp. 382-387
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